CN103145415A - Low-temperature sintered high-power antimony manganese-lead zirconate titanate piezoelectric ceramics - Google Patents

Abstract

The invention discloses a low-temperature sintered high-power ferroelectric antimony manganese-lead zirconate titanate piezoelectric ceramic, the raw material components and their mass percentage contents are: Pb _1.04 (Mn _1/3 Sb _2/3 ) _0.05 Zr _0.47 Based on Ti _0.48 O ₃ +0.15wt%SrCO ₃ +0.15wt%MnO ₂ , plus xwt.%CuO, where x=0.05~1.5; the present invention adopts the traditional solid phase synthesis method and is sintered at 900°C~1100°C. The invention realizes low-temperature sintering, has simple components and steps, is easy to operate, has good repeatability and high yield, and is very suitable for preparing piezoelectric transformers and transducers with single-layer or multi-layer structures (monolithic structures), and has many advantages. large market value.

Description

Low-temperature sintering high-power antimony-manganese-lead zirconate titanate piezoelectric ceramics

technical field

The invention relates to a ceramic composition characterized by components, in particular to a low-temperature sintered high-power antimony manganese-lead zirconate titanate piezoelectric ceramic material.

Background technique

Piezoelectric ceramics are functional ceramics that can convert mechanical energy and electrical energy, and belong to the category of inorganic non-metallic materials. Piezoelectric ceramic materials have excellent dielectric and piezoelectric properties, and the preparation process is simple and low cost. Therefore, electronic ceramics are a very key electronic information material. It is widely used in transducers, vibrators, transformers, sensors and other fields.

PZT-based piezoelectric ceramics have the characteristics of good piezoelectric performance, high Curie temperature, and excellent mechanical properties, so they occupy a dominant position in today's high-performance piezoelectric ceramics, but for PZT-based piezoelectric ceramics, its Most of the sintering temperatures are above 1200°C, causing the PbO in the raw materials to volatilize. On the one hand, the chemical composition of the ceramics will deviate from the stoichiometric ratio, which seriously affects the performance of piezoelectric ceramics. On the other hand, the volatilization of lead will also affect the human body. and adverse effects on the environment. In the current production, the main method to make up for lead volatilization is to use buried firing method, sealed sintering method or excessive PbO, none of which can fundamentally eliminate the volatilization of PbO, and the more effective method to suppress PbO volatilization is to realize piezoelectric ceramic material Low-temperature sintering, that is, reducing the sintering temperature of the piezoelectric ceramic material to below the temperature at which PbO volatilizes.

Since the 1990s, piezoelectric ceramic components are developing toward miniaturization, high performance, multi-function and integration in order to meet the needs of integrated circuit surface mount technology (SMT). The use of low temperature co-fired ceramics (LTCC) technology in SMT can increase assembly density, reduce volume, reduce weight, increase functions, improve reliability and performance, and shorten assembly cycle. Laminated ceramic composites are one of the hotspots of its research. At present, there are mainly two methods to realize the laminated structure. One is to fire a single piece and then bond it into a laminated structure. The other is to fire multiple layers at one time, using Pt and Pd noble metals as internal electrodes. The cost is expensive. In order to reduce the cost, the laminated structure device generally requires the use of Ag with good conductivity and low price as the internal electrode. Due to the low melting point of Ag, too high sintering temperature will cause silver ions to diffuse to the ceramic layer, thereby reducing the insulation resistance of ceramic materials. If low-temperature sintering of piezoelectric ceramic materials can be achieved, these two problems can be better solved.

At present, the main methods to achieve low-temperature sintering are as follows: (a) reduce the sintering temperature by adding flux, (b) reduce the sintering temperature by improving the powder making process, (c) reduce the sintering temperature by using hot pressing, (d) Microwave sintering was used to reduce the sintering temperature. Among them, the process of adding flux to reduce the sintering temperature is the simplest and the cheapest, and it is a method close to industrial production. By adding low-melting-point compounds to form a liquid phase at the initial stage of sintering, the mobility of grain boundaries can be improved due to the rearrangement of crystal grains and enhanced contact in liquid phase sintering, and the pores can be fully discharged, thereby promoting sintering densification and reducing the sintering temperature.

Based on this purpose, the present invention selects Pb _1.04 (Mn _1/3 Sb _2/3 ) Zr _0.47 Ti _0.48 O ₃ +0.15wt%SrCO ₃ +0.15wt%MnO ₂ piezoelectric ceramics as the research object, and adopts traditional solid-state reaction In this method, copper oxide (CuO) was selected as the dopant ion, and its influence on the structure and performance was studied, and the sintering temperature of the ceramic was reduced without deteriorating its piezoelectric and dielectric properties.

Contents of the invention

The object of the present invention is to adopt the traditional solid-phase synthesis preparation method, further reduce the sintering temperature on the basis of the prior art, and provide a low sintering temperature, antimony manganese-lead zirconate titanate piezoelectric material with good piezoelectric properties. electric ceramics.

The present invention is achieved through the following technical solutions:

Low-temperature sintering high-power ferroelectric antimony manganese-lead zirconate titanate piezoelectric ceramics, its raw material components and mass percentage content are: Pb _1.04 (Mn _1/3 Sb _2/3 ) _0.05 Zr _0.47 Ti _0.48 O ₃ +0.15 wt%SrCO ₃ +0.15wt%MnO ₂ as the basis, plus xwt.%CuO, where x=0.05~1.5;

The preparation method of the above-mentioned low-temperature sintered high-power ferroelectric antimony-manganese-lead zirconate titanate piezoelectric ceramics: use the method of solid phase synthesis, first pre-sinter the basic raw materials at 850 ° C, and finally sinter at 900 ° C ~ 1100 ° C, and keep warm for 2 hours.

The antimony manganese-zirconate titanate piezoelectric ceramic has a single perovskite structure.

The raw materials are Pb ₃ O ₄ , ZrO ₂ , TiO ₂ , MnO ₂ , Sb ₂ O ₃ , SrCO ₃ and CuO.

The beneficial effect of the present invention is to achieve low-temperature sintering (reducing the sintering temperature of PMS-PZT from 1180°C to 1240°C to 900°C to 930°C), and to maintain good piezoelectric performance, with a single additive CuO and low price , which meets the requirements of industrial production, and the lower sintering temperature suppresses the volatilization of PbO. Compared with other low-temperature sintering, the piezoelectric ceramics obtained by the present invention have superior performance and have great market value.

Description of drawings

Fig. 1 shows the influence of CuO doping amount on PMS-PZT dielectric loss tanδ at 900°C, 925°C, 1000°C, 1100°C for 2 hours of sintering and heat preservation;

Fig. 2 shows the influence of CuO doping amount on PMS-PZT piezoelectric coefficient d ₃₃ at 900°C, 925°C, 1000°C, 1100°C sintering and heat preservation for 2h;

Fig. 3 is the influence of CuO doping amount on PMS-PZT electromechanical coupling coefficient Kp at 900°C, 925°C, 1000°C, 1100°C sintering and heat preservation for 2h in the present invention;

的影响。Fig. 4 is the present invention at 900°C, 925°C, 1000°C, 1100°C for sintering and heat preservation for 2h, the effect of CuO doping amount on the dielectric constant of PMS-PZT

Impact.

Detailed ways

The present invention uses commercially available chemically pure raw materials (purity ≥ 99%), which are Pb ₃ O ₄ , ZrO ₂ , TiO ₂ , MnO ₂ , Sb ₂ O ₃ , SrCO ₃ and CuO.

The preparation method of low-temperature sintering high-power antimony manganese-lead zirconate titanate piezoelectric ceramics of the present invention is as follows:

(1) Ingredients

Based on Pb _1.04 (Mn _1/3 Sb _2/3 )Zr _0.47 Ti _0.48 O ₃ +0.15wt%SrCO ₃ +0.15wt%MnO ₂ , plus xwt.%CuO, where x=0.05~1.5, according to the above formula , Weigh the raw materials Pb ₃ O ₄ , ZrO ₂ , TiO ₂ , MnO ₂ , Sb ₂ O ₃ , SrCO ₃ and mix them, put them into a nylon tank, the ball milling medium is water and agate balls, the weight ratio of balls:material:water The mixture is 2:1:0.5, ball milled for 4 hours, the speed is 750 rpm, the mixture is dried in an oven at 90°C, then ground in a mortar, and passed through a 60-mesh sieve.

(2) pre-burning

Put the ground and sieved powder in step (1) into the crucible, compact it with an agate rod, cover it, seal it, heat it in a muffle furnace at a rate of 7°C/min to 850°C for 2 hours, and cool it down to room temperature naturally out of the oven.

(3) Secondary ball milling

According to the formula of step (1), take x=0.05, 0.1, 0.5, 1, 1.5, add CuO to the powder dried in step (2) for grinding, put it into a ball mill jar, add an appropriate amount of water, and ball mill for 4 hours, The rotation speed is 750 rpm, and then the powder is dried in an oven at 90°C.

(4) Granulation

Grind the powder dried in step (3) in a mortar, sieve, add PVA (polyvinyl alcohol) with a weight concentration of 7%, stir well, sieve, and put the powder into a stainless steel mold with a diameter of 35mm Inside, it is pressed into a cylindrical blank under a pressure of 100-120Mpa.

(5) Molding

Put the cylindrical blank after granulation in step (4) to stand for 24 hours, grind it, pass through a 60m sieve, put the powder into a stainless steel mold with a diameter of 12mm, and press it into a cylindrical blank under a pressure of 400Mpa.

(6) Glue removal

Put the blank in step (5) into a muffle furnace, raise the temperature of the blank to 200°C at a rate of 3°C/min, then raise the temperature from 200°C to 400°C at a rate of 1.5°C/min, and keep it at 400°C for 30 minutes , raised to 650°C at a rate of 5°C/min and held for 10 minutes to discharge organic matter.

(7) Sintering

Put the organic matter blanks from step (6) into the crucible, seal it, and use PMS-PZT powder as the embedding material to bury and burn. ℃ for 2 hours, and naturally cooled to room temperature with the furnace.

(8) Burning electrodes

Polish the ceramic sheet sintered in step (7) to a thickness of 1mm, dry it naturally, coat the upper and lower surfaces with silver paste by screen printing process, place it in a muffle furnace and heat it up to 735°C for 10min. Naturally cool to room temperature.

(9) Test dielectric and piezoelectric properties.

Specific embodiments of the present invention are shown in Table 1.

Table 1

Concrete testing means of the present invention: use the WAYNEKERR4225 type LCR automatic measuring instrument of China Tianjin Radio No. 6 Factory, measure the loss tangent tan δ and electric capacity C of sample at room temperature, measuring frequency is 1kHz, and relative permittivity ε _r value is given by Calculated as follows:

$\frac{{\mathrm{<span\; class="notranslate">\; \&epsiv;</span>}}_{\mathrm{<span\; class="notranslate">\; 33</span>}}^{\mathrm{<span\; class="notranslate">\; T</span>}}}{{\mathrm{<span\; class="notranslate">\; \&epsiv;</span>}}_{\mathrm{<span\; class="notranslate">\; 0</span>}}}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; 4</span>}\mathrm{<span\; class="notranslate">\; C</span>}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; h</span>}}{{\mathrm{<span\; class="notranslate">\; \&epsiv;</span>}}_{\mathrm{<span\; class="notranslate">\; 0</span>}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; \&pi;</span>}{\mathrm{<span\; class="notranslate">\; D.</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}$

In the formula: ε ₀ - vacuum dielectric constant, its value is 8.854×10 ^-12 F/m; C - capacitance, unit is F; h - sample thickness, unit m; π - circular ratio; here take 3.1416; D - Sample diameter, in m.

According to the national standard GB11309-89, the present invention adopts the ZJ-3A quasi-static tester of the Institute of Acoustics, Chinese Academy of Sciences to test the piezoelectric coefficient d ₃₃ , the unit of which is pCN ^-l .

The electromechanical coupling coefficient K _P obtained in the present invention is obtained by looking up the Kp table comprehensively through the difference between resonance and anti-resonance frequency Δf=f _a -f _r and Poisson's ratio σ, and Poisson's ratio σ is calculated by the following formula of:

$\mathrm{<span\; class="notranslate">\; \&sigma;</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; 5.332</span>}{\mathrm{<span\; class="notranslate">\; f</span>}}_{\mathrm{<span\; class="notranslate">\; r</span>}}<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 1.867</span>}{\mathrm{<span\; class="notranslate">\; f</span>}}_{\mathrm{<span\; class="notranslate">\; r</span>}\mathrm{<span\; class="notranslate">\; 1</span>}}}{\mathrm{<span\; class="notranslate">\; 0.6054</span>}{\mathrm{<span\; class="notranslate">\; f</span>}}_{\mathrm{<span\; class="notranslate">\; r</span>}\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 1.191</span>}{\mathrm{<span\; class="notranslate">\; f</span>}}_{\mathrm{<span\; class="notranslate">\; r</span>}}}$

f _r is the resonant frequency, f _a is the anti-resonant frequency, f _r1 is the primary overtone resonant frequency, f _r , f _a , and f _r1 all use the resonant-anti-resonant method to generate high-frequency signals using the XFG-7 of Shanghai Yamei Electric Appliance Factory measured by the device.

随着不同CuO掺杂量的变化趋势很相似，均出现先增大后减小的趋势，并都在掺杂量为0.1wt.%时取得最大值。最佳性能参数在CuO掺杂量0.1wt.%时925℃煅烧取得，分别为d₃₃=289pC/N，kp=56%，

tanδ=0.41%。It can be seen from Figure 1 that the sample loss shows a trend of first decreasing and then increasing with the increase of CuO doping amount. It can be seen from accompanying drawings 2, 3 and 4 that the d ₃₃ , Kp and

The trend of change with different CuO doping amounts is very similar, both appear to increase first and then decrease, and all reach the maximum value when the doping amount is 0.1wt.%. The best performance parameters are obtained by calcination at 925°C when the CuO doping amount is 0.1wt.%, respectively, d ₃₃ =289pC/N, kp=56%,

tanδ=0.41%.

The piezoelectric ceramic material prepared by applying the present invention is mainly used in piezoelectric transformers and transducers with a single-layer or multi-layer structure (monolithic structure).

The above description of the embodiments is to facilitate the understanding and application of the present invention by those of ordinary skill in the technical field. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative efforts. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention should fall within the protection scope of the present invention.

Claims (5)

1. high-power ferroelectric antimony manganese-lead titanate piezoelectric ceramics of low-temperature sintering, its feed composition and mole percent level thereof are Pb _1.04(Mn _1/3Sb _2/3) _0.05Zr _0.47Ti _0.48O ₃, adding on this basis mass percent is 0.15wt%SrCO ₃With 0.15wt%MnO ₂, then to add on the basis of the above mass percent be xwt.%CuO, wherein x=0.05～1.5.

The preparation method of the high-power ferroelectric antimony manganese-lead titanate piezoelectric ceramics of above-mentioned low-temperature sintering: adopt the method for solid phase synthesis, first basic material is given burning, 900 ℃ the most finally ~ 1100 ℃ sintering, insulation 2h in 850 ℃.

2. according to claim 1 the high-power antimony manganese-lead titanate piezoelectric ceramics of low-temperature sintering, is characterized in that, described antimony manganese-zirconium metatitanic acid piezoelectric ceramics is single perovskite structure.

3. according to claim 1 the high-power antimony manganese-lead titanate piezoelectric ceramics of low-temperature sintering, is characterized in that, described raw material is Pb ₃O ₄, ZrO ₂, TiO ₂, MnO ₂, Sb ₂O ₃, SrCO ₃And CuO.

4. according to claim 1 the high-power antimony manganese-lead titanate piezoelectric ceramics of low-temperature sintering, is characterized in that, the preferred value that adds xwt.%CuO is x=0.1.

5. according to claim 1 the high-power antimony manganese-lead titanate piezoelectric ceramics of low-temperature sintering, is characterized in that, preferred sintering temperature is 925 ℃.

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